EP1971567A1 - Method of purifying (meth)acrylates - Google Patents

Method of purifying (meth)acrylates

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Publication number
EP1971567A1
EP1971567A1 EP06807162A EP06807162A EP1971567A1 EP 1971567 A1 EP1971567 A1 EP 1971567A1 EP 06807162 A EP06807162 A EP 06807162A EP 06807162 A EP06807162 A EP 06807162A EP 1971567 A1 EP1971567 A1 EP 1971567A1
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EP
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Prior art keywords
meth
acrylates
purification
isocyanate
polymerization
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Granted
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EP06807162A
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German (de)
French (fr)
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EP1971567B1 (en
Inventor
Bardo Schmitt
Joachim Knebel
Günther Gräff
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Roehm GmbH Darmstadt
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Evonik Roehm GmbH
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Publication of EP1971567A1 publication Critical patent/EP1971567A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation

Definitions

  • the invention relates to a process for reducing the alcohol content in (meth) acrylates and their uses.
  • (Meth) acrylates have a wide variety of applications.
  • (Meth) acrylates are monomers which can be reacted in polymerization reactions, for example, to polymethacrylates. But (meth) acrylate polymers can also be used as a binder or additive in paints, coatings, coatings, etc. Also in the pharmaceutical industry (meth) acrylates are used in the form of their polymers, for example for coating tablets. High purity is usually very beneficial.
  • JP 2003261509 describes a transesterification in the presence of Sn catalysts.
  • the reaction mixture is treated with acidic ion exchange resin.
  • JP 01052747 describes the preparation of isocyanate-containing methacrylates. For purification, it is distilled and the removal of Cl-containing impurities is carried out using a molecular sieve (NaA zeolite). However, only hydrolysable compounds can be removed by this process.
  • JP 2003048866 describes a transesterification in the presence of titanates and the treatment with alumina for catalyst removal.
  • the object of the invention was to produce (meth) acrylates in high purity and with high yields.
  • the object has been achieved by a process for working up (meth) acrylates, characterized in that an isocyanate / catalyst mixture is added and then distilled.
  • isocyanates it is possible to use all mono- or polyfunctional isocyanates. Preference is given to all customary diisocyanates, such as toluene diisocyanate, hexane diisocyanate, isophorodiisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate.
  • isocyanate activators can be used.
  • amines more preferably diazabicyclooctane, are used.
  • organotin compounds are also preferred, particularly preferably dioctyltin oxide, tin dilaurate or tin diethylhexanoate.
  • the isocyanate / catalyst mixture is composed of the calculated amount of isocyanate and 0.01 to 1% of catalyst based on the weighed monomer.
  • the isocyanate is added in equimolar amounts, but preferably in excess, to the concentration of the impurities, such as water and / or alcohol.
  • the ratio is from 1: 1 to 10: 1, more preferably for diisocyanates at 1: 1 (isocyanate: impurity).
  • the purification takes place in two steps. First, the (meth) acrylates are stirred at 60 to 90 ° C., preferably at 80 ° C., for 1 to 6 hours after the addition of isocyanates.
  • the (meth) acrylates are distilled.
  • the distillation takes place as a function of (meth) acrylate at atmospheric pressure or under vacuum.
  • the distillation is preferably carried out under conditions of 60 to 140 ° C. and 0.1 to 10 mbar.
  • the notation (meth) acrylate as used herein means both methacrylate, e.g. Methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, e.g. Methyl acrylate, ethyl acrylate, etc., as well as mixtures of both.
  • the particularly low residual alcohol content allows many fields of use of the (meth) acrylates purified by the present process.
  • these (meth) acrylates can be used in anionic polymerizations, group transfer polymerization (GTP), ATRP, RAFT and all polymerization techniques that are sensitive to contaminants.
  • GTP group transfer polymerization
  • ATRP ATRP
  • RAFT RAFT
  • all polymerization techniques that are sensitive to contaminants.
  • the approach is weighed.
  • the monomers are mixed with 50-100 ppm HQME (hydroquinone monomethyl ether).
  • the product is distilled through a column. After a forerun, the main fraction is obtained as methacrylate / product.
  • the batch is weighed without catalyst and the isocyanate in a molar excess, compared with the sum of residual alcohol and water content, added.
  • the monomers are mixed with 50-100 ppm HQME (hydroquinone monomethyl ether). After stirring for three hours at approx. 80 ° C, the product is distilled through a column. After a forerun, the main fraction is obtained as methacrylate / reduced alcohol product.
  • the batch is weighed in and the isocyanate is added in molar excess compared to the sum of residual alcohol and water content.
  • the monomers are mixed with 50-100 ppm HQME (hydroquinone monomethyl ether). After three hours of stirring at about 80 0 C, the product is distilled through a column. After a forerun, the main fraction is obtained as methacrylate / product with minimized alcohol content.
  • the batch is weighed in and the isocyanate is added in molar excess compared to the sum of residual alcohol and water content.
  • the monomers are mixed with 50-100 ppm HQME (hydroquinone monomethyl ether). After three hours of stirring at about 80 0 C, the product is over a Distilled column. After a forerun, the main fraction is obtained as methacrylate / product with minimized alcohol content.
  • Comparative Example 1 shows that normal column distillation does not result in improved product quality in terms of residual alcohol content.
  • Comparative Example 2 shows that a treatment of the starting material with isocyanate without the usual isocyanate catalyst, followed by column distillation also leads to no product improvement.
  • Examples 3 to 7 show that a work-up of the (meth) acrylates according to the invention leads to a minimization of the residual alcohol content and thus to an optimization of the product quality.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Purifying methacrylate (I) comprises adding an isocynate/catalyst mixture and subsequently distilling the obtained mixture.

Description

Verfahren zur Aufreinigung von (Meth)acrylaten Process for the purification of (meth) acrylates
Die Erfindung betrifft ein Verfahren zur Reduzierung des Alkoholgehaltes in (Meth)acrylaten und deren Verwendungen.The invention relates to a process for reducing the alcohol content in (meth) acrylates and their uses.
(Meth)acrylate haben die verschiedensten Anwendungsbereiche. (Meth)acrylate sind Monomere, die in Polymerisationsreaktionen beispielsweise zu Polymethacrylaten umgesetzt werden können. (Meth)acrylatpolymere können aber auch als Bindemittel oder Additiv in Farben, Lacken, Beschichtungen usw. eingesetzt werden. Auch in der pharmazeutischen Industrie werden (Meth)acrylate in Form ihrer Polymeren beispielsweise zur Beschichtung von Tabletten genutzt. Eine hohe Reinheit ist zumeist sehr vorteilhaft.(Meth) acrylates have a wide variety of applications. (Meth) acrylates are monomers which can be reacted in polymerization reactions, for example, to polymethacrylates. But (meth) acrylate polymers can also be used as a binder or additive in paints, coatings, coatings, etc. Also in the pharmaceutical industry (meth) acrylates are used in the form of their polymers, for example for coating tablets. High purity is usually very beneficial.
In der Literatur findet man viele Wege, (Meth)acrylate zu reinigen. Neben der Destillation werden die Behandlung mit Adsorbentien und die Extraktion mit Lösungsmitteln beschrieben.There are many ways to purify (meth) acrylates in the literature. In addition to the distillation, the treatment with adsorbents and the extraction with solvents are described.
In der JP 2003261509 wird eine Umesterung in Gegenwart von Sn- Katalysatoren beschrieben. Zur Katalysatorentfernung wird das Reaktionsgemisch mit saurem lonentauscherharz behandelt.JP 2003261509 describes a transesterification in the presence of Sn catalysts. For catalyst removal, the reaction mixture is treated with acidic ion exchange resin.
In der JP 01052747 wird die Herstellung von isocyanathaltigen Methacrylaten beschrieben. Zur Aufreinigung wird destilliert und zur Entfernung von Cl- haltigen Verunreinigungen wird mit einem Molsieb (NaA Zeolith) gearbeitet, Mit diesem Verfahren können jedoch nur hydrolisierbare Verbindungen entfernt werden. JP 2003048866 beschreibt eine Umesterung in Gegenwart von Titanaten und die Behandlung mit Tonerde zur Katalysatorentfernung.JP 01052747 describes the preparation of isocyanate-containing methacrylates. For purification, it is distilled and the removal of Cl-containing impurities is carried out using a molecular sieve (NaA zeolite). However, only hydrolysable compounds can be removed by this process. JP 2003048866 describes a transesterification in the presence of titanates and the treatment with alumina for catalyst removal.
Aufgabe der Erfindung war es (Meth)acrylate in hoher Reinheit und mit hohen Ausbeuten herzustellen.The object of the invention was to produce (meth) acrylates in high purity and with high yields.
Die Aufgabe wurde gelöst durch ein Verfahren zur Aufarbeitung von (Meth)acrylaten, dadurch gekennzeichnet, dass eine Isocyanat/Katalysator- Mischung zugegeben und anschließend destilliert wird.The object has been achieved by a process for working up (meth) acrylates, characterized in that an isocyanate / catalyst mixture is added and then distilled.
Es wurde gefunden, dass das erhaltene Produkt nur geringe Mengen an Alkohol enthält. Mit herkömmlichen Aufreinigungsverfahren konnten Restalkoholgehalte unter 0,1 Gew.-% nicht dargestellt werden. Für viele empfindliche Reaktionen, wie beispielsweise anionische Polymerisationen, ist dies ein zu hoher Restalkoholgehalt. Mit dem erfindungsgemäßen Verfahren können Restalkoholgehalte von < 0,01 Gew.-% erreicht werden.It has been found that the product obtained contains only small amounts of alcohol. With conventional purification processes residual alcohol contents below 0.1 wt .-% could not be displayed. For many sensitive reactions, such as anionic polymerizations, this is too high a residual alcohol content. With the process according to the invention, residual alcohol contents of <0.01% by weight can be achieved.
Überraschend wurde gefunden, dass die Aufarbeitung stabil verläuft. Es werden keine Polymerisate als Verunreinigung gefunden, denn eine Nebenreaktion der Isocyanate mit den phenolischen Stabilisatoren war zu befürchten.Surprisingly, it has been found that the work-up is stable. There are no polymers found as an impurity, because a side reaction of the isocyanates with the phenolic stabilizers was to be feared.
Es wurde gefunden, dass die Reinheiten erhöht werden konnten, in Abhängigkeit vom Edukt teilweise auf 99,9%.It was found that the purities could be increased, depending on the educt partially to 99.9%.
Es wird eine Isocyanat/Katalysator-Mischung verwendet.An isocyanate / catalyst mixture is used.
Als Isocyanate können alle mono- oder polyfunktionellen Isocyanate verwendet werden. Bevorzugt werden alle gängigen Diisocyanate, wie Toluoldiisocyanat, Hexandiisocyanat, Isophorodiisocyanat, 2,2,4-Trimethylhexamethylen- diisocyanat, Diphenylmethandiisocyanat, Dicyclohexylmethandiisocyanat.As isocyanates, it is possible to use all mono- or polyfunctional isocyanates. Preference is given to all customary diisocyanates, such as toluene diisocyanate, hexane diisocyanate, isophorodiisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate.
Als Katalysatoren können alle bekannten Isocyanataktivatoren verwendet werden. Vorzugsweise werden Amine, besonders bevorzugt Diazabicyclooctan, verwendet. Bevorzugt werden aber auch zinnorganische Verbindungen, besonders bevorzugt Dioctylzinnoxid, Zinndilaurat oder Zinndiethylhexanoat, eingesetzt.As catalysts, all known isocyanate activators can be used. Preferably, amines, more preferably diazabicyclooctane, are used. However, organotin compounds are also preferred, particularly preferably dioctyltin oxide, tin dilaurate or tin diethylhexanoate.
Die Isocyanat/Katalysator-Mischung ist zusammengesetzt aus der berechneten Menge Isocyanat und 0,01 bis 1 % Katalysator, bezogen auf das eingewogene Monomer.The isocyanate / catalyst mixture is composed of the calculated amount of isocyanate and 0.01 to 1% of catalyst based on the weighed monomer.
Das Isocyanat wird in äquimolaren Mengen, bevorzugt aber im Überschuss, zur Konzentration der Verunreinigungen, wie Wasser und/oder Alkohol, zugegeben.The isocyanate is added in equimolar amounts, but preferably in excess, to the concentration of the impurities, such as water and / or alcohol.
Das Mengenverhältnis liegt bei 1 :1 bis 10:1 , besonders bevorzugt für Diisocyanate bei 1 :1 (Isocyanat : Verunreinigung).The ratio is from 1: 1 to 10: 1, more preferably for diisocyanates at 1: 1 (isocyanate: impurity).
Die Aufreinigung erfolgt in zwei Schritten. Zuerst werden die (Meth)acrylate bei 60 bis 90 0C, vorzugsweise bei 80 0C 1 bis 6 Stunden nach der Zugabe von Isocyanaten gerührt.The purification takes place in two steps. First, the (meth) acrylates are stirred at 60 to 90 ° C., preferably at 80 ° C., for 1 to 6 hours after the addition of isocyanates.
Anschließend werden die (Meth)acrylate destilliert. Die Destillation erfolgt in Abhängigkeit vom (Meth)acrylat bei Normaldruck oder unter Vakuum. Bevorzugt wird die Destillation bei Bedingungen von 60 bis 140 0C und 0.1 bis 10 mbar durchgeführt.Subsequently, the (meth) acrylates are distilled. The distillation takes place as a function of (meth) acrylate at atmospheric pressure or under vacuum. The distillation is preferably carried out under conditions of 60 to 140 ° C. and 0.1 to 10 mbar.
Die Schreibweise (Meth)acrylat bedeutet hier sowohl Methacrylat, wie z.B. Methylmethacrylat, Ethylmethacrylat usw., als auch Acrylat, wie z.B. Methylacrylat, Ethylacrylat usw., sowie Mischungen aus beiden.The notation (meth) acrylate as used herein means both methacrylate, e.g. Methyl methacrylate, ethyl methacrylate, etc., as well as acrylate, e.g. Methyl acrylate, ethyl acrylate, etc., as well as mixtures of both.
Der besonders niedrige Restalkoholgehalt ermöglicht viele Einsatzgebiete der mit dem vorliegenden Verfahren aufgereinigten (Meth)acrylate. Vorzugsweise können diese (Meth)acrylate in anionische Polymerisationen, der Group Transfer Polymerisation (GTP), ATRP, RAFT und allen Polymerisationstechniken, die empfindlich gegenüber Verunreinigungen sind, verwendet werden. Die im Folgenden gegebenen Beispiele werden zur besseren Veranschaulichung der vorliegenden Erfindung gegeben, sind jedoch nicht dazu geeignet, die Erfindung auf die hierin offenbarten Merkmale zu beschränken.The particularly low residual alcohol content allows many fields of use of the (meth) acrylates purified by the present process. Preferably, these (meth) acrylates can be used in anionic polymerizations, group transfer polymerization (GTP), ATRP, RAFT and all polymerization techniques that are sensitive to contaminants. The examples given below are given for a better illustration of the present invention, but are not intended to limit the invention to the features disclosed herein.
BeispieleExamples
Vergleichsbeispiel 1 (VB 1):Comparative Example 1 (VB 1):
1600,0 g Ethylhexylmethacrylat, enthaltend 0,040 mol Wasser und 0,160 mol Ethylhexanol1600.0 g of ethylhexyl methacrylate containing 0.040 mol of water and 0.160 mol of ethylhexanol
Der Ansatz wird eingewogen. Die Monomere sind mit 50 -100 ppm HQME (Hydrochinonmonomethylether) versetzt. Das Produkt wird über eine Kolonne destilliert. Nach einem Vorlauf wird die Hauptfraktion als Methacrylat/Produkt erhalten.The approach is weighed. The monomers are mixed with 50-100 ppm HQME (hydroquinone monomethyl ether). The product is distilled through a column. After a forerun, the main fraction is obtained as methacrylate / product.
Vergleichsbeispiel 2 (VB 2):Comparative Example 2 (VB 2):
1600,0 g Ethylhexylmethacrylat, enthaltend 0,070 mol Wasser und1600.0 g of ethylhexyl methacrylate containing 0.070 mol of water and
0,130 mol Ethylhexanol 78,9 g = 0,47 mol Hexamethylendiisocyanat0.130 mol of ethylhexanol 78.9 g = 0.47 mol of hexamethylene diisocyanate
Der Ansatz wird ohne Katalysator eingewogen und das Isocyanat im molaren Überschuss, verglichen mit der Summe aus Restalkohol und Wassergehalt, versetzt. Die Monomere sind mit 50 -100 ppm HQME (Hydrochinonmonomethylether) versetzt. Nach drei Stunden Rühren bei ca. 80°C wird das Produkt über eine Kolonne destilliert. Nach einem Vorlauf wird die Hauptfraktion als Methacrylat/Produkt mit reduziertem Alkoholgehalt erhalten.The batch is weighed without catalyst and the isocyanate in a molar excess, compared with the sum of residual alcohol and water content, added. The monomers are mixed with 50-100 ppm HQME (hydroquinone monomethyl ether). After stirring for three hours at approx. 80 ° C, the product is distilled through a column. After a forerun, the main fraction is obtained as methacrylate / reduced alcohol product.
Beispiel 3 (B 3):Example 3 (B 3):
1580,0 g Ethylhexylmethacrylat, enthaltend 0,040 mol Wasser und1580.0 g of ethylhexyl methacrylate containing 0.040 mol of water and
0,160 mol Ethylhexanol 33,6 g = 0,2 mol Hexamethylendiisocyanat 1 ,6 g Zinn-Il-Ethylhexanoat (0,1 % bez. auf Ethylhexylmethacrylat)0.160 mol of ethylhexanol 33.6 g = 0.2 mol of hexamethylene diisocyanate 1.6 g of tin-1-ethylhexanoate (0.1% based on ethylhexyl methacrylate)
Der Ansatz wird eingewogen und das Isocyanat im molaren Überschuss, verglichen mit der Summe aus Restalkohol und Wassergehalt, versetzt. Die Monomere sind mit 50 -100 ppm HQME (Hydrochinonmonomethylether) versetzt. Nach drei Stunden Rühren bei ca. 800C wird das Produkt über eine Kolonne destilliert. Nach einem Vorlauf wird die Hauptfraktion als Methacrylat/Produkt mit minimiertem Alkoholgehalt erhalten.The batch is weighed in and the isocyanate is added in molar excess compared to the sum of residual alcohol and water content. The monomers are mixed with 50-100 ppm HQME (hydroquinone monomethyl ether). After three hours of stirring at about 80 0 C, the product is distilled through a column. After a forerun, the main fraction is obtained as methacrylate / product with minimized alcohol content.
Beispiel 4 (B 4):Example 4 (B 4):
1600,0 g Butyldiglykolmethacrylat, enthaltend 0,070 mol Wasser und1600.0 g of butyl diglycol methacrylate containing 0.070 mol of water and
0,045 mol Butyldiglykol0.045 mol of butyldiglycol
19,3 g = 0,115 mol Hexamethylendiisocyanat 1 ,6 g Zinn-Il-Ethylhexanoat (0,1 % bez. auf Butyldiglykolmethacrylat)19.3 g = 0.115 mol of hexamethylene diisocyanate 1.6 g of tin-¹-ethylhexanoate (0.1% based on butyl diglycol methacrylate)
Der Ansatz wird eingewogen und das Isocyanat im molaren Überschuss, verglichen mit der Summe aus Restalkohol und Wassergehalt, versetzt. Die Monomere sind mit 50 -100 ppm HQME (Hydrochinonmonomethylether) versetzt. Nach drei Stunden Rühren bei ca. 800C wird das Produkt über eine Kolonne destilliert. Nach einem Vorlauf wird die Hauptfraktion als Methacrylat/Produkt mit minimiertem Alkoholgehalt erhalten.The batch is weighed in and the isocyanate is added in molar excess compared to the sum of residual alcohol and water content. The monomers are mixed with 50-100 ppm HQME (hydroquinone monomethyl ether). After three hours of stirring at about 80 0 C, the product is over a Distilled column. After a forerun, the main fraction is obtained as methacrylate / product with minimized alcohol content.
Alle weiteren Versuche sind analog berechnet. Ansatzberechnung;All further experiments are calculated analogously. Approach calculation;
Analytik:analytics:
Vergleichsbeispiel 1 zeigt, dass eine normale Kolonnendestillation nicht zu einer verbesserten Produktqualität hinsichtlich des Restalkoholgehalts führt.Comparative Example 1 shows that normal column distillation does not result in improved product quality in terms of residual alcohol content.
Vergleichsbeispiel 2 zeigt, dass eine Behandlung des Ausgangsmaterials mit Isocyanat ohne den üblichen Isocyanat-Katalysator mit anschließender Kolonnendestillation ebenfalls zu keiner Produktverbesserung führt.Comparative Example 2 shows that a treatment of the starting material with isocyanate without the usual isocyanate catalyst, followed by column distillation also leads to no product improvement.
Beispiele 3 bis 7 zeigen, dass eine erfindungsgemäße Aufarbeitung der (Meth)acrylate zu einer Minimerung des Restalkoholgehalts und damit zu einer Optimierung der Produktqualität führen. Examples 3 to 7 show that a work-up of the (meth) acrylates according to the invention leads to a minimization of the residual alcohol content and thus to an optimization of the product quality.

Claims

Patentansprüche claims
1. Verfahren zur Aufreinigung von (Meth)acrylaten, dadurch gekennzeichnet, dass eine Isocyanat/Katalysator-Mischung zugegeben und anschließend destilliert wird.1. A process for the purification of (meth) acrylates, characterized in that an isocyanate / catalyst mixture is added and then distilled.
2. Verfahren zur Aufreinigung von (Meth)acrylaten nach Anspruch 1 , dadurch gekennzeichnet, dass mono- oder polyfunktionelle Isocyanate verwendet werden.2. A process for the purification of (meth) acrylates according to claim 1, characterized in that mono- or polyfunctional isocyanates are used.
3. Verfahren zur Aufreinigung von (Meth)acrylaten nach Anspruch 1 , dadurch gekennzeichnet, dass Isocyanataktivatoren oder zinnorganische Verbindungen verwendet werden.3. A process for the purification of (meth) acrylates according to claim 1, characterized in that Isocyanataktivatoren or organotin compounds are used.
4. Verfahren zur Aufreinigung von (Meth)acrylaten nach Anspruch 3, dadurch gekennzeichnet, dass Amine oder Dioctylzinnoxid, Zinndilaurat oder Zinndiethylhexanoat verwendet werden.4. A process for the purification of (meth) acrylates according to claim 3, characterized in that amines or dioctyltin oxide, tin dilaurate or Zinndiethylhexanoat be used.
5. Verfahren zur Aufreinigung von (Meth)acrylaten nach Anspruch 1 , dadurch gekennzeichnet, dass das Isocyanat im äquimolaren Verhältnis oder im Überschuss zur Konzentration der Verunreinigung zugegeben wird.5. A process for the purification of (meth) acrylates according to claim 1, characterized in that the isocyanate is added in equimolar ratio or in excess of the concentration of the impurity.
6. Verfahren zur Aufreinigung von (Meth)acrylaten nach Anspruch 5, dadurch gekennzeichnet, dass das Isocyanat im Verhältnis von 1 :1 bis 10:1 eingesetzt wird.6. A process for the purification of (meth) acrylates according to claim 5, characterized in that the isocyanate in a ratio of 1: 1 to 10: 1 is used.
7. Verwendung von (Meth)acrylaten hergestellt gemäß Anspruch 1 in Polymerisationsverfahren.7. Use of (meth) acrylates prepared according to claim 1 in polymerization.
8. Verwendung von (Meth)acrylaten hergestellt gemäß Anspruch 1 in der anionischen Polymerisation, der Group Transfer Polymerisation (GTP), ATRP, RAFT und allen Polymerisationsverfahren, die empfindlich gegenüber Verunreinigungen sind. 8. Use of (meth) acrylates prepared according to claim 1 in anionic polymerization, group transfer polymerization (GTP), ATRP, RAFT and all polymerization processes that are sensitive to impurities.
EP06807162A 2006-01-12 2006-10-11 Method of purifying (meth)acrylates Not-in-force EP1971567B1 (en)

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DE102006001771A DE102006001771A1 (en) 2006-01-12 2006-01-12 Purifying methacrylate, useful e.g. in polymerization process, preferably anionic polymerization and group transfer polymerization, comprises adding an isocyanate/catalyst mixture and subsequently distilling the obtained mixture
PCT/EP2006/067293 WO2007087903A1 (en) 2006-01-12 2006-10-11 Method of purifying (meth)acrylates

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EP1971567B1 (en) 2011-07-27
TW200738622A (en) 2007-10-16
US7750179B2 (en) 2010-07-06
US20080300373A1 (en) 2008-12-04
ATE517858T1 (en) 2011-08-15
JP2009523145A (en) 2009-06-18
JP4922310B2 (en) 2012-04-25
WO2007087903A1 (en) 2007-08-09
DE102006001771A1 (en) 2007-07-19
CN101309892A (en) 2008-11-19

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